EP0321066B1 - All-in-one boiler water treatment composition - Google Patents

All-in-one boiler water treatment composition Download PDF

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Publication number
EP0321066B1
EP0321066B1 EP88303437A EP88303437A EP0321066B1 EP 0321066 B1 EP0321066 B1 EP 0321066B1 EP 88303437 A EP88303437 A EP 88303437A EP 88303437 A EP88303437 A EP 88303437A EP 0321066 B1 EP0321066 B1 EP 0321066B1
Authority
EP
European Patent Office
Prior art keywords
sodium
water
acid
sulfite
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88303437A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0321066A2 (en
EP0321066A3 (en
Inventor
Llye H. Steimel
Ronald J. Christensen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIVERSEY Corp
Original Assignee
Diversey Corp Canada
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Diversey Corp Canada filed Critical Diversey Corp Canada
Priority to AT88303437T priority Critical patent/ATE78242T1/de
Publication of EP0321066A2 publication Critical patent/EP0321066A2/en
Publication of EP0321066A3 publication Critical patent/EP0321066A3/en
Application granted granted Critical
Publication of EP0321066B1 publication Critical patent/EP0321066B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances

Definitions

  • a boiler requires extremely pure water in order to avoid a plurality of different problems. Unfortunately water available for most boilers is not pure enough to avoid these problems. Untreated water would rapidly damage the boiler eventually destroying it.
  • Phosphates are typically used as an internal treatment for scale prevention in boilers. Basically this forms a sludge that is easily removed.
  • Other scale preventers includes low molecular weight polymers generally in combination with phosphates and the like. Polymethacrylates and polyacrylates having molecular weights around 4500 have also been used for scale. These act not only to prevent scale formation but also in certain applications can act as descalants. Polymaleic acid is also employed.
  • Oxygen pitting is typically solved by removal of oxygen in the make-up water. A large amount of oxygen dissolved in water can be removed by physical treatment, dearation. Subsequent chemical treatment by oxygen scavengers is then required to remove the last traces of oxygen. There are several different oxygen scavengers. Hydrazine is a commonly employed scavenger. Unfortunately, generated steam containing hydrazine is unsuitable for applications where the steam may contact food. Other less dangerous chemicals typically used include sulfites such as sodium sulfite and erythorbic acid. The use of this composition is disclosed for example in U.S. Patent 4,419,327. It is also known to use ascorbic acid but this treatment is not commonly employed.
  • Other chemicals used to treat boiler water include sodium hydroxide which increases alkalinity and precipitates magnesium, sodium carbonate which also increases alkalinity and precipitates calcium, and magnesium, chelants such as ethylenediaminetetraacetic acid, tannins, starches, lignins, carboxymethylcellulose which prevents feed line deposits, sodium nitrate which inhibits caustic embrittlement and antifoaming agents.
  • sodium hydroxide which increases alkalinity and precipitates magnesium
  • sodium carbonate which also increases alkalinity and precipitates calcium
  • magnesium chelants such as ethylenediaminetetraacetic acid, tannins, starches, lignins, carboxymethylcellulose which prevents feed line deposits, sodium nitrate which inhibits caustic embrittlement and antifoaming agents.
  • the general object of the invention is to provide an all-in-one treatment composition which provides a balanced scale prevention and removal, sludge treatment, oxygen scavenging, metal passivation, condensate treatment as well as iron and magnesium control.
  • a concentrated all-in-one boiler water treatment composition in accordance with the invention is characterised in that it comprises, by weight, Glucoheptonate 0% to 0.2% Sulfite 0.1% to 14% Polyhydroxy acid 0.1 to 5% Diethylaminoethanol 0.0 to 15.0% 1st polymer 0.1 to 4% Polymaleate 0.01 to 4% Carbonate 0 to 7% Water soluble base 0 to 20% Water to 100% the sulfite being sodium or potassium sulfite; the 1st polymer is a polymethacrylate or polyacrylate; the carbonate is sodium carbonate or potassium carbonate and the polyhydroxy acid is an ascorbic acid or erythorbic acid.
  • Such a composition includes an alkalinity control agent, condensate treatment particularly diethylaminoethanol, oxygen scavengers particularly sodium sulfite and a polyhydroxy acid. Further, the composition preferably includes a polymer system including a water soluble polymethacrylate and water soluble polymaleic acid, both neutralized in this system.
  • Such a composition can be provided at high concentrations for storage and application and is effective at use concentrations.
  • the composition comprises, by weight, Sodium Glucoheptonate 0.01 to 0.2% Sodium Sulfite 1.0 to 10% Sodium Carbonate 0.01 to 7% Ascorbic Acid 0.1 to 5% Polymethacrylate having a molecular weight of 500-5000 0.1 to 4% Polymaleate acid having a molecular weight of 500-1000 0.1 to 4% Diethylaminoethanol 0.1 to 15% Sodium hydroxide 10 to 20% Water to 100%
  • a carbonate cycle treatment composition in accordance with the invention includes an oxygen scavenging system, a condensate treatment, a hardness and scale prevention and removal system as well as an iron control agent. These are mixed and stored as a concentrated aqueous mixture and added to the boiler water to provide effective treatment.
  • the following description provides the desired use concentrations of each component of this system.
  • the all-in-one treatment composition is formed by adding concentrated forms of these components at relative concentrations so that the formulated treatment composition can be dispensed into the boiler water and attain the desired use concentrations for all of these components.
  • the actual amount of each chemical added to the concentrated formulations depends on the precise intended use concentrations and the concentration of each chemical when purchased.
  • the oxygen scavenging/condensate control mechanism is a three component system.
  • the system includes a sulfite, a polyhydroxy acid and diethylaminoethanol.
  • Effective sulfites include sodium and potassium sulfite and sodium and potassium bisulfite.
  • the use concentration of sodium or potassium sulfite should range from about 20 to about 60 ppm. Since the sulfite is consumed, the concentrated solution will include a slight excess of sulfite, generally 45 to 90 ppm is applied.
  • the polyhydroxy acid is a water soluble acid preferably erythorbic acid or ascorbic acid. Ascorbic acid is preferred over erythorbic acid since it acts synergistically with the diethylaminoethanol to provide effective oxygen scavenging.
  • the concentration of polyhydroxy acid should be from about 1 to about 40 parts per million. Again, ascorbic acid is consumed in the boiler. So a slight excess is applied generally up to 100 ppm with 10-20 ppm preferred.
  • Sufficient DEAE is provided to neutralize the acid and to provide a condensate pH of 7.5-8.5. To provide both condensate treatment and neutralization of the acid generally 1-200 ppm DEAE is required. Preferably the use concentration will be 25 to 50 ppm. If no condensate treatment is necessary, the DEAE need not be included.
  • the hardness control is provided through three components.
  • the first of these components is sodium carbonate or potassium carbonate which reacts with the hardness to form calcium carbonate which can easily be removed.
  • sodium carbonate or potassium carbonate which reacts with the hardness to form calcium carbonate which can easily be removed.
  • Some carbonate can be provided by the natural water so slightly less carbonate is applied. Thus, the applied concentration should range from 0 ppm to 500 ppm.
  • first and a second low molecular weight polymer should be employed.
  • the first polymer is preferably the sodium neutralized salt of polymethacrylate or polyacrylate having a molecular weight of from 500 to 5000.
  • the second polymer is preferably a polymaleate having a molecular weight of from 500 to 1000.
  • the polymethacrylates and polyacrylates can be obtained in a wide range of molecular weights, but generally the molecular weight should range from 500 to 5000 with 4500 being preferred.
  • the most preferred is polymethacrylate having a pH of about 11.5 with a molecular weight of about 4500. This is employed at about 1 to 80 parts per million with 12-24 ppm being preferred.
  • the polymaleate is added as polymaleic acid and is neutralized in the solution to form the corresponding sodium or potassium polymaleate.
  • the polymaleate can have a molecular weight generally from about 500 to 1000 with 750 being the preferred molecular weight. This is used at a concentration of 1 to 80 parts per million with about 5-10 parts per million being preferred.
  • composition of the present invention includes a glucoheptonate, preferably a sodium or potassium glucoheptonate to transport iron out of the system. This would be used at a range of 0 to 10 parts per million with 1-2 parts per million being preferred.
  • the composition also includes a water soluble base generally sodium or potassium hydroxide if needed to bring the pH of the boiler water to about 11-11.5.
  • a water soluble base generally sodium or potassium hydroxide if needed to bring the pH of the boiler water to about 11-11.5.
  • the concentrate will include 10-15% sodium hydroxide depending on the pH of the make up of water in the boiler.
  • the concentrated form of this treatment composition includes as actives by weight DEAE 0 to 15% Polymaleate 0.1 to 4% Polymethacrylate 0.1 to 4% Polyhydroxy acid 0.1 to 5% Soda Ash 0 to 7% Sulfite 1 to 14% Glucoheptonate 0 to 0.2% Water soluble base 0 to 15% Water to 100%
  • At least 0.1% DEAE should be present in the concentrate.
  • the preferred formulation is, by weight, Water 77.6% Sodium hydroxide 8.5% DEAE 2.6% Polymaleate 0.5% Polymethacrylate 1.2% Ascorbic Acid 0.5% Na2CO3 4.5% Sodium Sulfite 4.5% Sodium Glucoheptonate 0.1%
  • This concentrated formulation is formed by simply mixing the components.
  • the boiler water composition of the present invention is used at the above use concentrations. In its concentrated form, it is generally about 80-90% water. It is dispensed periodically to the boiler water to provide the concentrations as listed above. Generally 1000 to 2000 ppm of this formulation is added to and maintained in the boiler. This treatment is useful in low pressure applications generally in boilers operating at less than 250 psi (1.7 x 106 N/m2)
  • the above preferred formulation was used to treat three five hundred horse power (370 kW) boilers having a 50% condensate return operating at 12 psi (82 kN/m2) with continuous blow down.
  • the make up water has an M alkalinity as CaCO3 of 52mg/l, a total hardness of CaCO3 of less than 1mg/l, chloride at 25mg/l, sulfate at 89mg/l and a conductance of 378 with a pH of 7.2.
  • the water conditions of the steam boiler and condensate from week 1 to week 8 were as follows:
  • the boiler treatment composition of the present invention maintained a very high condensate pH and boiler sulfite residual.
  • the maximum pH the equipment could test at was 8.3 to 8.4. This pH is met and in most applications exceeded with this treatment program.
  • a 150 horsepower (110 kW) Cleaver Brooks boiler was tested operating at 90 psi (620 kN/m2) with no continuous blow down. Dual tank softeners were employed.
  • the boiler operates one hour per day on hard water. Prior to use of the present invention the boiler included 1/4 to 1/8 inch (6.5 to 3.2 mm) scale deposits over the entire tube surface. Iron oxide in the hematite state covered over 50% of the surface. The scale consisted of 13.2% iron as Fe2O3, 39.6% calcium as CaO, 13.5% silica as SiO2, 25.0% phosphate as P2O5, and 4.7% carbonate.
  • the make up water in this system had an M alkalinity as CaCO3 of 152mg/l, a total hardness as CaCO3 of less than 1mg/l 23 hours per day and 80mg/l for one hour a day, the chloride was 28mg/l and silica as SiO2 of 0.3mg/l.
  • the sulphate as SO4 was 70mg/l and conductance was 490 with a pH of 8.2.
  • the conditions of the steam boiler and condensate from week 1 to week 8 were as follows:
  • the treatment of the present invention raised the pH from 5.1 or less to a pH of 7.5 in a long condensate system typical of a hospital.
  • the good pH readings along with poor control of the cycle of concentrations indicate that if the system were better controlled the pH readings would be excellent to great.
  • the present invention did a good job in a system with an excess of 150 M alkalinity at 90 psi. (620 kN/m2).
  • the above composition was used on a 100 horsepower (74 kW) North America boiler having a condensate sample cooler. There was no continuous blow down and a single tank softener generally less than 2 parts per million total hardness. Prior to the test this boiler had a low condensate pH generally less than 5.
  • the make up water had an M alkalinity as CaCO3 of 95mg/l, a total hardness as CaCO3 of less than 1mg/l, chloride 23mg/l, silica as SiO2 6mg/l, sulphate as SO4 6mg/l, TDS 360mg/l and pH 7.4.
  • the water conditions of the steam boiler and condensate from week 1 to week 8 were as follows: The composition of the present invention did an excellent job in raising the condensate pH from 5.3 to over 7.7 and lowering the free CO2 to less than 3mg/l.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
EP88303437A 1987-12-16 1988-04-15 All-in-one boiler water treatment composition Expired - Lifetime EP0321066B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88303437T ATE78242T1 (de) 1987-12-16 1988-04-15 Alles enthaltende zusammensetzung fuer die behandlung von kesselwasser.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13350487A 1987-12-16 1987-12-16
US133504 1987-12-16

Publications (3)

Publication Number Publication Date
EP0321066A2 EP0321066A2 (en) 1989-06-21
EP0321066A3 EP0321066A3 (en) 1989-09-20
EP0321066B1 true EP0321066B1 (en) 1992-07-15

Family

ID=22458925

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88303437A Expired - Lifetime EP0321066B1 (en) 1987-12-16 1988-04-15 All-in-one boiler water treatment composition

Country Status (8)

Country Link
EP (1) EP0321066B1 (enrdf_load_stackoverflow)
JP (1) JPH01171697A (enrdf_load_stackoverflow)
AT (1) ATE78242T1 (enrdf_load_stackoverflow)
AU (1) AU598440B2 (enrdf_load_stackoverflow)
CA (1) CA1306661C (enrdf_load_stackoverflow)
DE (1) DE3872849T2 (enrdf_load_stackoverflow)
ES (1) ES2051840T3 (enrdf_load_stackoverflow)
GR (1) GR3005899T3 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8784679B2 (en) 2011-10-25 2014-07-22 Dubois Chemicals, Inc. Aqueous powder water treatment compositions and methods for making same

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9005440D0 (en) * 1990-03-10 1990-05-09 Ciba Geigy Ag Composition
US5091108A (en) * 1991-02-21 1992-02-25 Nalco Chemical Company Method of retarding corrosion of metal surfaces in contact with boiler water systems which corrosion is caused by dissolved oxygen
JP3172744B2 (ja) * 1992-12-25 2001-06-04 栗田工業株式会社 ボイラ用薬剤
US6797197B2 (en) * 2002-08-30 2004-09-28 Johnsondiversey, Inc. Modified amine for boiler water treatment
KR101284809B1 (ko) * 2007-06-15 2013-07-10 에스케이케미칼주식회사 수처리제 조성물 및 이를 이용한 수처리 방법
JP2009285530A (ja) * 2008-05-27 2009-12-10 Kurita Water Ind Ltd ボイラ装置用水処理剤及びボイラ装置の水処理方法
JP5786277B2 (ja) * 2010-03-31 2015-09-30 栗田工業株式会社 スケール除去方法及びスケール除去剤

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5242748A (en) * 1975-10-01 1977-04-02 Hitachi Ltd Process for detecting the position and shape of an object
JPS55109210A (en) * 1979-02-09 1980-08-22 Kurita Water Ind Ltd Stabilizer for aqueous sulfite solution
US4443340A (en) * 1981-10-09 1984-04-17 Betz Laboratories, Inc. Control of iron induced fouling in water systems
GB2117369B (en) * 1982-04-01 1985-02-27 Nalco Chemical Co Sulfite-erythorbic acid corrosion inhibitors
JPS6059080A (ja) * 1983-09-08 1985-04-05 Kurita Water Ind Ltd 腐食抑制剤
US4609483A (en) * 1985-03-07 1986-09-02 W. R. Grace & Co. Scale inhibiting composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8784679B2 (en) 2011-10-25 2014-07-22 Dubois Chemicals, Inc. Aqueous powder water treatment compositions and methods for making same

Also Published As

Publication number Publication date
ES2051840T3 (es) 1994-07-01
GR3005899T3 (enrdf_load_stackoverflow) 1993-06-07
AU2651288A (en) 1989-06-22
JPH01171697A (ja) 1989-07-06
AU598440B2 (en) 1990-06-21
DE3872849D1 (de) 1992-08-20
ATE78242T1 (de) 1992-08-15
EP0321066A2 (en) 1989-06-21
DE3872849T2 (de) 1992-12-03
CA1306661C (en) 1992-08-25
EP0321066A3 (en) 1989-09-20

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